Oils of the Coniferae. II—The Leaf and Twig, and Bark Oils of White Fir

Oils of the Coniferae. II—The Leaf and Twig, and Bark Oils of White Fir. A. W. Schorger. Ind. Eng. Chem. , 1914, 6 (10), pp 809–810. DOI: 10.1021/...
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Oct., 1914

T H E J O r R A V A L O F I N D L-STRI.1 L A R D E A V G I N E . E R I S G C H E M I S T R Y

ha\-e found the a p p a r a t u s shown in Fig. I t o be quite satisfactory. T h e precipitate is susceptible t o oxidation a n d must be kept a w a y from air during drying. Also,'the fact t h a t high temperature will char t h e soap limits t h e drying temperature t o about 80' C. T h e precipitate m a y be dried in a desiccator connected b y a long rubber tubing t o a source of hydrogen or carbon dioxide, and t o a vacuum p u m p . After introducing t h e precipitate t o be dried, t h e desiccator m a y be placed in a low-temperature s t e a m drying oven for 3 hours. T h e results obtained b y t h e use of t h e insoluble-soap method a n d t h e d a t a from which these results were computed, are compiled in Table 11. I n calculating t h e results for this table it was decided t o accept t h e weight of t h e dried insoluble soap a s representative of t h e weight of wood oil present in t h e sample, since the FIG I error of this assumption was considered t o be within t h e limits of error 0; t h e method. Although neither of t h e above methods has proved entirely satisfactory a s a method for t h e estimation of wood oil in rosin varnishes. t h e efforts made t o apply t h e m t o t h a t end have resulted in some interesting d a t a regarding t h e conditions existing in this t y p e of varnish. TABLE 11-Ex

PRECIPITATIOV OF INSOLUBLE POTASSIUM SOAP U r 0 O D OIL 7 ADULTERANT CalReSAMPLE ADULTERANT cu- covFound c--Soap lated ered Present Xo G G Kind G G C 7 , G 7 7c 1 3.301 3 . 3 3 4 3 . 3 3 4 101.0 -0,033 -1.0 12.8140'304) 2.807 2 , 8 0 7 9 9 . 8 0.311 9.9 4:s 1 3 . 0 1 2 0 . 1 8 0 Linseed 3.021 3 . 0 2 1 1 0 0 . 3 0.171 5.5 5.6 1 2.516 0 . 5 0 6 ( 2.508 2 , 5 0 8 9 9 . 8 0.514 17.0 16.7 1 3 138 .... 3 , 1 7 0 3 , 1 7 0 1 0 1 . 0 -0.032 -1 0 1 2:859 0 : 9 5 9 Soya 2.874 2.874 100.6 0.944 24.7 2 3 : 8 1 2.6420.881)bean 2 . 6 4 5 2.645 100.1 0.878 24.9 2 5 . 0 1 3.013 . . . . .... 3.006 3 , 0 0 6 99.8 0,007 0.2 1 3 , 0 0 6 0 , 1 6 7 Soya 2 . 9 8 2 2.982 9 9 . 2 0.191 6.0 5:3 1 7 . 0 5 1 1 . 3 0 2 1 bean 2.020 2.020 98.1 1.333 39.8 38.9 1 2.461 0 . 1 2 5 , 2 . 5 3 6 2.536 1 0 3 . 0 -0.075 2.9 4.8 1 2 . 7 9 1 0 . 6 0 7 ~2.883 ~ ~2.E(83 ~ ~1 0 3~. 3 ~ 0~. 5 1 5 15.2 1 7 . 9 1 2.742 0 380 2.761 2 . 1 6 1 100.7 0.361 11.5 12.2 1 2.742 0 183; 2.741 2.741 1 0 0 . 0 0.184 6.3 6.3 1 2.528 . . . .., . 2 . 5 0 1 2.501 9 8 . 9 0,027 1.1 .. 1 2.524 ... .... 2 , 5 5 0 2 . 5 5 0 101.0 -0,026 -1.0 .. 1 2.521 . . . .... 2 . 5 1 0 2.510 9 9 . 5 0.011 0.5 1 2.510 2.514 2.514 1 0 0 . 2 -0.004 -0.2 12.3210:iOil 2.367 2.367 102.0 0.661 2 1 . 8 22:4 1 2 . 4 2 8 0 738jLinseed 2 . 5 0 8 2 . 5 0 8 103.3 0.658 20.8 23.3 1 3.019 ,... 3 . 0 1 9 3 . 0 1 9 100.0 I 3.039 o : ~ O Y Mixed 3.025 3.025 99.5 0:4i3 12:3 i i : 9 1 3.199 1.049) .3.201 3 . 2 0 1 100.3 1.038 2 4 . 5 2 4 . 7 2 3.252 . . .. .. 3.224 3.224 99.1 0.028 0.9 .. 3 3.471 . . .... 5 . 5 4 4 3 . 5 4 4 1 0 2 . 1 -0.073 -2.1 .. 4 3.1.56 . . .,, 3 , 0 1 4 3.014 95.5 0,142 4.5 ., 4 3.190 . . . . ,,. 3,092 3.092 96.9 0.098 3.1 .. NuTE-XVood oils Nos. 1 2 a n d 3 were t h e same a s those in Table I . Wood oil No. 4 was furnished'by M r . L. P. Nemzek representing t h e Educational Bureau of t h e Paint Manufacturers' Association. This oil is f r o m American-grown n u t s , %MITATION B Y

809

A comparison of t h e molecular weights of t h e f a t t y acids from raw wood oil a n d t h e light breaks seems t o show t h a t this light break is a n isomer rather t h a n a polymer, a n d t h a t there is practically no difference between t h e light break formed slowly b y sunlight alone a n d t h a t catalyzed b y iodine. USIVERSITY OF ICZICHIGAW ANN ARBOR ~

OILS OF THE CONIFERAE. 11-THE LEAF AND TWIG, AND BARK OILS OF WHITE FIR By A . \V. SCHORGER

Received August 15. 1914

T h e white fir [ A b i e s concolor (Gord.) P a r r y J is found on t h e mountain slopes from southern Oregon t o Lower California and from Nevada, U t a h , a n d southern Colorado through Arizona and New Mexico. T h e dense crown consists of short, heavily foliaged branches. T h e leaves a t t h e t o p of t h e tree are usually I t o I l i g inches in length, while those of t h e lower branches are somewhat longer-1 ljg t o 3 inches. L E A F A X D TTVIG O I L S

T h e oils were greenish yellow in color with a green fluorescence with t h e exception of samples Nos. 2439 a n d 2487, which were lemon-yellow in color and showed no fluorescence. The residue left after removal of t h e terpenes b y distillation was fluorescent t o a marked degree, b u t this property was n o t noted in t h e "green oil" fraction obtained, though the oil owes its green color t o this fraction. T h e properties of t h e oils and the yields are given in Table I. TABLEI-PROPERTIES

7 m

7

Sample No. dijo

n

2176 2180 2181 2183 2439 2440 2487

1.4788 1.4786 1.4786 1.4796 1.4787 1.4790 1.4781

~

" "

0 8758 0.8738 0.8732 0.8737 0.8720 0.8745 0.8777

OF OILS Ester No. AcePer cent Yield of oil aftet t a t e alcohol Acid Ester acetyl- Per -APer --~e~~~~ ~ o KO. S o . ation cent Free Total cent LEAF A N D TWIGOILS -27.94 1.13 12.52 48.88 4.38 10.28 13.73 0.140 -20.18 1.81 27.34 54.58 9.57 7.65 15.17 0.029 -21.65 1.43 24.03 52.45 $41 7.99 14.60 0.050 -26.87 1.07 20.55 54.22 t.19 9.50 15.15 0.150 -26.59 1.01 14.48 51.83 5.07 10.57 14.55 0.163 -24.08 1.32 14.80 47.84 5.18 9.32 13.39 0.095 -20.11 1.06 18.79 55.51 6.58 10.39 15.56 0.272

_______

Mean, 6.63 9.39

14.59 0.128

BARK OILS OLDiOo

2209 0.8i67 1.4833 -20.95 2423 0.8702 1.4809 -20.15

1.22 0.87

6.88 23.34 2.41 6.43 20.45 2.25 ~

Mean, 2.33

4.58 3.90

6.48 0.07 5.67 0.12

4.24

6.08 0.095

-

-

" "

An examination of t h e separated constituents of a Chinese-wood-oil rosin varnish seems t o show t h a t t h e polymerization of wood oil in t h e presence of rosin is practically a s complete as in t h e oil, subject t o t h e same heat t r e a t m e n t in t h e absence of rosin. T h e f a t t y acid in each case shows a molecular weight double t h a t of t h e f a t t y acid of r a w wood oil. T h e difference in characteristics between these t w o polymerized products h a s not a s yet been satisfactorily accounted for.

There is a considerable variation in t h e ester a n d free alcohol content in t h e various samples b u t t h e t o t a l alcohol content is fairly uniform. Samples Nos. 2439 a n d 2440 were distilled from material taken from t h e top a n d base, respectively, of t h e same tree. T h e needles from t h e t o p of t h e tree show a slightly greater total alcohol content. Six hundred grams of oil distilled as follows: 1611 6 j o , 1 j . j per cent: 16j-1joo1 4 2 per cent; 1 7 0 - 1 8 0 ° , 1 8 . j per c e n t ; 18*19j", 3 per cent; 1 g j - - 2 4 0 ~ , 1 3 per c e n t ; z40-310", 3 per cent. IDENTIPICATIOS O F CONSTITUEKTS

FURFURAL-The first fraction was shaken out with water. On treating t h e aqueous extract with aniline and hydrochloric acid a deep crimson color characteristic of furfural was obtained. a-PISEh?z-The fraction examined for a-pinene h a d

T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y

810

Vol. 6, KO. I O

t h e following properties: B. p . 156.5'-I j 9 . o o , d160 in ether. T h e oil was emerald-green i n color a n d 0.8671, aD220 -24.29'. T h e nitrosochloride separated showed no fluorescence. N o solid derivatives were very slowly from t h e mother liquor. T h e purified obtained. This oil appears t o be similar t o t h e "green compound melted at 103' a n d i t s nitrolpiperidine at oil" obtained b y t h e author from t h e leaf oil of Douglas 118.5'. T h e t o t a l fractions boiling below 160' fir1 a n d showed t h e same color reactions. a m o u n t e d t o 75 g. (12.5 per c e n t ) . BARK OIL CAMPHENE-The camphene fraction b. p. 160-164' T h e b a r k distilled was a b o u t one-quarter of a n inch a m o u n t e d t o 8 per cent. T h e fraction b . p . 160-162', thick a n d h a d been peeled from small trees cut for poles. dlSo 0.8695, aD230-27.390, was tested according t o t h e T h e properties of t h e oils a n d t h e yields are given i n m e t h o d of B e t r a m a n d Walbaum.' On treating t h e Table I. T h e following results were obtained on distillation saponified product with water t h e isoborneol separated 65 per cent; b. p . a s a viscous oil. On s t e a m distillation oil first passed of I I O g. of oil: b. p. 162.5-170', 170-180', 14 per c e n t ; b . p . 180-192', 8 per c e n t ; over, followed b y isoborneol t h a t solidified i n t h e con192-2joo, 4 per c e n t ; 2j0-3oo0, 5 per cent. denser. T h e purified isoborneol melted a t 209-210' i n a sealed t u b e . T h e fraction b. p. 1 6 ~ - 1 6 4 ~ . y i e l d e d IDENTIFICATION O F COKSTITUENTS smaller a m o u n t s of isoborneol. FURFURAL-This aldehyde was detected i n t h e first P-PINENE-This terpene is t h e major constituent fraction b y t h e color method. F r o m t h e intensity of of t h e leaf oil, since 254 g. (42.3 per cent) were finally color produced a larger q u a n t i t y of furfural is present obtained boiling between 164-170'. On oxidation of i n t h e bark oil t h a n i n t h e leaf a n d twig oil. -23.66', CX-PINENE-BY repeated fractionation I O g. (9.1 per a fraction, b. p. 164-166.5', dl50 0 . 8 7 1 5 , aD230 cent) of oil were obtained of b. p. 160-163', cyD2o9 with alkaline potassium permanganate, large quantities of sodium nopinate were obtained. T h e free nopinic -16.43'. This oil yielded 2.1 g. (21 per cent) of pinene acid melted at 126.6-127'. nitrosochloride. I t s nitrolpiperidine melted a t I 18 '. PHELLASDRENE-The fractions b . p . 170-180 ', P-PINENE_The &pinene fractions distilled a s folweighing 90 g., gave large a m o u n t s of phellandrene lows: ( I ) b. p . 163-16j0, 14.9 g . ; ( 2 ) b . p . 16j-17oo, nitrite. T h e fraction b . p. 174-177'~ d150 0.8572, j 1 . 2 g. T h e l a t t e r fraction h a d dlso 0.8654, ~i~~~~ aD220 -28.74', formed a solid mass of crystals on t r e a t - - 2 2 . j 2 O . On oxidation of t h e oil a yield of 2 1 . 7 per m e n t with KNOz a n d acetic acid. T h e nitrite melted cent of sodium nopinate was obtained. T h e free at 1 0 2 ' . Limonene was not detected a s either t h e nopinic acid melted a t 126-127'. Five grams of dihydrochloride or tetrabromide. sodium nopinate yielded 24 per cent of nopinone, BORNEOL-The oil obtained b y saponification of t h e whose semicarbazone melted a t 188'. fraction b. p . 200-240' distilled i n a b o u t equal proDIPENTENE-The oil boiling between I 70-180' h a d portions between 2 0 j - 2 1 j o a n d 2 1 5-220'. T h e first t h e rotation -29.37'. On treating t h e d r y oil portion h a d t h e rotation cyD24o -29.16'. Both frac- with d r y HC1 gas a dihydrochloride m. p. 49-jo' was tions were t r e a t e d with phthalic anhydride. Sapon- obtained, b u t no solid derivative was obtained on ification of t h e phthalic esters yielded oils. On bromination. oxidizing t h e l a t t e r with chromic acid mixture camphor A L C O H O L FRACTIOP-The a m o u n t of oil obtained by was obtained melting a t I 7 1-1 7 2 '. Considerably saponification of t h e fraction b. p. 192-2j0° was too larger yields of camphor were obtained b y oxidizing small for identification of t h e alcohol present. T h e t h e borneol fraction directly with s a t u r a t e d potassium ester a n d free alcohol h a v e been calculated as bornyl permanganate solution without a t t e m p t i n g i t s puri- acetate a n d borneol as i t is most probable t h a t these are fication through t h e phthalic ester. T h e camphor was t h e constituents present. converted t o i t s semicarbazone melting at 236-237'. ' ( G R E E NoIL"-The fraction b . p. 2 j0-3oo0, weighing A C E T I C ACID-The acids recovered from t h e ester 5.4 g., was bright green i n color a n d from i t s color saponification liquors were precipitated as their silver reactions appeared identical with t h e "green oil" from salts in five fractions. Analysis of portions of t h e t h e leaf a n d twig oil. I t is possible t h a t t h e "green various precipitates without further purification gave a oil" i n t h e leaf a n d twig oil is n o t derived from t h e silver content of 63.04-63.72 per cent, showing t h a t needles themselves, b u t from t h e b a r k of t h e twigs. acetic acid must be practically t h e only acid present, SUMMARY since *silver propionate theoretically requires 59.91 T h e oils of white fir have approximately t h e following per cent Ag, silver acetate 64.64 per cent Ag, a n d silver composition. formate 70.59 per cent Ag. T h e combined precipitates Leaf a n d TxIig oil Bark oil Percentages Trace Trace Furfural were recrystallized from water several times. T h e fine 9 12 l - ~ - P i n e n e. . . . . . . . . . . needles obtained were analyzed as follows: 8 I-Camphene . . . . . . . . . . 60 42 1-0-Pinene.. . . . . . . . . . . 0.1140 g. silver salt gave 0.0736 g. Ag = 64.56 per Dipentene 12-13 15 l-Phellandrene . . . . . . . . 2.5 6.5 Ester as bornyl acetate cent Ag. 4.5 9.5 +e borneol.. . . . . . . . 5 3 Green oil". . . . . . . . . . . " G R E E K oIL"-The residue remaining after removal 7 4 Losses,. . . . . . . . . . . . . . of t h e ester fraction h a d a strong green fluorescence. FOREST PRODUCTS LABORATORY T h e fraction b. p . 240-31oO on redistillation distilled FOREST SERVICE, U. S. DEPARTMENT OF AGRICULTURE mainly between 265-285'. I t h a d d19.50 0.925, (In Cooperation with the University of Wisconsin) &1.4DISON nDIs01.4936, an200-o.490, for a 37.83 per cent solution 1

Jour. frlr prakt. Chem., [Z] 49 (1894), 1.

1

J o u r . A m . Chem. Soc., 95 (1913), 1895-7.